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Framework Isomerism in Vanadium Metal-Organic Frameworks: MIL-88B(V) and MIL-101(V)
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
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2013 (English)In: Crystal Growth & Design, ISSN 1528-7483, E-ISSN 1528-7505, Vol. 13, no 11, 5036-5044 p.Article in journal (Refereed) Published
Abstract [en]

Two families of metal organic frameworks (MOFs), MIL-88 and MIL-101 built by trinuclear transition metal (TM) clusters (TM = Cr, Fe, or Sc), have been known for several years, but their syntheses are often reported separately. In fact, these MOFs are polymorphs, or framework isomers: they are assembled from the same metal secondary building units and organic linkers, but the connectivity of these components differs. Here we report for the first time the synthesis of the vanadium MOF MIL-88B(V) and compare its synthesis parameters to those of MIL-47(V) and the recently reported MIL-101(V). The properties of MIL-88B(V) and MIL-101(V) are remarkably different. MIL-88B(V) can breathe and is responsive to different solvents, while MIL-101(V) is rigid and contains mesoporous cages. MIL-101(V) exhibits the highest specific surface area among vanadium MOFs discovered so far. In addition, both MIL-88B(V) and MIL-101(V) transform to MIL-47 at higher temperatures. We have also identified the key synthesis parameters that control the formation of MIL-88B(V), MIL-101(V), and MIL-47: temperature, time, and pH. This relates to the rate of reaction between the metal and linkers, which has been monitored by ex situ X-ray powder diffraction and V K-edge X-ray absorption spectroscopy during MOF synthesis. It is therefore important to fully study the synthesis conditions to improve our understanding of framework isomerism in MOFs.

Place, publisher, year, edition, pages
2013. Vol. 13, no 11, 5036-5044 p.
National Category
Chemical Sciences
Research subject
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-97390DOI: 10.1021/cg4012058ISI: 000326775000050OAI: oai:DiVA.org:su-97390DiVA: diva2:678085
Funder
Swedish Research CouncilVINNOVAKnut and Alice Wallenberg Foundation
Note

AuthorCount:7;

Available from: 2013-12-11 Created: 2013-12-09 Last updated: 2017-12-06Bibliographically approved
In thesis
1. Development of Metal–Organic Frameworks for Catalysis: Designing Functional and Porous Crystals
Open this publication in new window or tab >>Development of Metal–Organic Frameworks for Catalysis: Designing Functional and Porous Crystals
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Metal–organic frameworks, or MOFs, have emerged as a new class of porous materials made by linking metal and organic units. The easy preparation, structural and functional tunability, ultrahigh porosity, and enormous surface areas of MOFs have led to them becoming one of the fastest growing fields in chemistry. MOFs have potential applications in numerous areas such as clean energy, adsorption and separation processes, biomedicine, and sensing. One of the most promising areas of research with MOFs is heterogeneous catalysis.

This thesis describes the design and synthesis of new, carboxylate-based MOFs for use as catalysts. These materials have been characterized using diffraction, spectroscopy, adsorption, and imaging techniques. The thesis has focused on preparing highly-stable MOFs for catalysis, using post-synthetic methods to modify the properties of these crystals, and applying a combination of characterization techniques to probe these complex materials.

In the first part of this thesis, several new vanadium MOFs have been presented. The synthesis of MIL-88B(V), MIL-101(V), and MIL-47 were studied using ex situ techniques to gain insight into the synthesis–structure relationships. The properties of these materials have also been studied.

In the second part, the use of MOFs as supports for metallic nanoparticles has been investigated. These materials, Pd@MIL-101–NH2(Cr) and Pd@MIL-88B–NH2(Cr), were used as catalysts for Suzuki–Miyaura and oxidation reactions, respectively. The effect of the base on the catalytic activity, crystallinity, porosity, and palladium distribution of Pd@MIL-101–NH2(Cr) was studied.

In the final part, the introduction of transition-metal complexes into MOFs through different synthesis routes has been described. A ruthenium complex was grafted onto an aluminium MOF, MOF-253, and an iridium metallolinker was introduced into a zirconium MOF, UiO-68–2CH3. These materials were used as catalysts for alcohol oxidation and allylic alcohol isomerization, respectively.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockkholm University, 2015. 144 p.
Keyword
Metal–organic frameworks, heterogeneous catalysis, nanoparticles, metallolinkers, postsynthetic modification, postsynthetic exchange
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-115819 (URN)978-91-7649-166-9 (ISBN)
External cooperation:
Public defence
2015-06-05, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 5: Manuscript.

Available from: 2015-05-13 Created: 2015-04-01 Last updated: 2016-08-26Bibliographically approved

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